POLYGRAM - POLYisotopologues of GReenhouse gases: Analysis and Modelling

Lead Research Organisation: Royal Holloway University of London
Department Name: Earth Sciences


The greenhouse gases carbon dioxide (CO2) and methane (CH4) are by far the biggest contributors to recent and ongoing climate change. Of all the known greenhouse gases (excluding water vapour), CO2 and CH4 have the highest concentrations in the atmosphere and they are rising rapidly. CO2 is particularly problematic because there is so much of it (about 200 times more than CH4) and because once emitted to the atmosphere, much of it will stay there for several hundred years. Whereas, by comparison, CH4 has a lifetime in the atmosphere of about a decade, but it is a much more potent greenhouse gas than CO2 - that is, for equal amounts of CO2 and CH4 in the atmosphere, CH4 will trap heat radiation about 70 times more effectively than CO2 (over a 20-year time period).

With the ratification of the Paris Agreement, the world has committed to avoiding dangerous climate change and the most obvious way to do this is by reducing emissions of CO2 and CH4. How will we know if emission mitigation policies are effective? Which nations or regions are meeting their emissions reduction targets? How will natural CO2 and CH4 fluxes respond to extreme weather events? And which aspects of the carbon cycle remain unsolved? For example, despite decades of study, scientists are still not sure why CH4 emissions are currently rising. To answer these questions we need to be able to measure and quantify CO2 and CH4 emissions and concentrations, and have the ability to separately quantify natural and manmade sources. Our current abilities to do so are severely limited, especially for CH4, which has a diverse array of natural and manmade sources. If we cannot determine the effectiveness of mitigation policies, then our ability to predict climate change impacts will be compromised by large uncertainties.

'Polyisotopologues' are one very promising new tool for distinguishing between different source emissions. The chemical elements that make up CO2 and CH4 molecules (carbon (C), oxygen (O) and hydrogen (H)) can have different masses, called isotopes. Different sources can have different isotopic 'fingerprints' or 'signatures' (because source reaction processes may favour a lighter or heavier molecule), thus measuring isotopic signatures is a useful way to gain insight into sources. Isotopic measurements have been made routinely for several decades; whereas the state-of-the-art technology developed in this project would allow us to measure molecules with more than one rare isotope. For example, most C has a relative atomic mass of 12 and H a mass of 1. The rarer isotopes of C and H have masses of 13 and 2, respectively. Isotopologues of CH4, which are measured routinely, include 12CH4, 13CH4 and 12CH3D (where 'D' represents the heavy H atom with mass 2). Whereas polyisotopologues of CH4 include 13CH3D and 12CH2D2 - these are far more challenging to measure, yet could provide invaluable insight into source emissions and sinks.

POLYGRAM (POLYisotopologues of GReenhouse gases: Analysis and Modelling) will push the frontiers for both CO2 and CH4 polyisotopologue measurement capability using the latest advances in laser spectroscopic analysis and very high-resolution isotope ratio mass spectrometry. In addition to these challenging technological developments, we will establish a small global atmospheric sampling network to examine latitudinal and longitudinal variations in polyisotopologues, which will help us to constrain overall global budgets of CO2 and CH4. We will carry out field campaigns to determine polyisotopologue source signatures, for example, of CH4 from wetlands, cattle and landfills, and of CO2 from plant photosynthesis and respiration, and from fossil fuel burning. We will conduct laboratory experiments to estimate the reaction rates for CH4 isotopologues when they are oxidised and destroyed in the atmosphere. Finally, we will carry out atmospheric transport modelling for both gases to better interpret and understand the measurements.


10 25 50
publication icon
Nisbet EG (2023) Slaying the methane minotaur. in Proceedings of the National Academy of Sciences of the United States of America

publication icon
Woolley Maisch C (2023) Methane Source Attribution in the UK Using Multi-Year Records of CH 4 and d 13 C in Journal of Geophysical Research: Atmospheres

Description isoMET - Metrology for European Emissions Verification on Methane Isotopes, EU Green Deal 2021 Metrology Partnership Research and Innovation Actions
Amount £25,836 (GBP)
Funding ID UKRI 10054154 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 09/2022 
End 09/2025